US3184413A - Polymeric lubricating oil additives containing iodine and uses thereof - Google Patents

Polymeric lubricating oil additives containing iodine and uses thereof Download PDF

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US3184413A
US3184413A US204043A US20404362A US3184413A US 3184413 A US3184413 A US 3184413A US 204043 A US204043 A US 204043A US 20404362 A US20404362 A US 20404362A US 3184413 A US3184413 A US 3184413A
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iodine
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lubricating oil
copolymer
polymeric
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Michael J Furey
Zaybekian Philip
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ExxonMobil Technology and Engineering Co
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M1/00Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants
    • C10M1/08Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants with additives
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00Chemical modification by after-treatment
    • C08F8/18Introducing halogen atoms or halogen-containing groups
    • C08F8/20Halogenation
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/04Elements
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/026Butene
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/04Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing aromatic monomers, e.g. styrene
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/06Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing conjugated dienes
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28Esters
    • C10M2207/282Esters of (cyclo)aliphatic oolycarboxylic acids
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28Esters
    • C10M2207/34Esters having a hydrocarbon substituent of thirty or more carbon atoms, e.g. substituted succinic acid derivatives
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/084Acrylate; Methacrylate
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/086Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type polycarboxylic, e.g. maleic acid
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/02Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
    • C10M2219/024Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds of esters, e.g. fats
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2225/00Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2225/04Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions obtained by phosphorisation of macromolecualr compounds not containing phosphorus in the monomers
    • C10M2225/041Hydrocarbon polymers
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/02Bearings

Definitions

  • This invention relates to lubricant additives. More specifically, this invention relates to polymeric lubricant additives containing iodine.
  • Lubricant additives containing iodine and prepared according to the present invention will find utility wherever lubricant additives having antifriction, antiwear, and EP properties are desired, e.g., automobile crankcase lubrication, bearing lubrication, gear lubrication, etc.
  • the treatment with iodine may be made by contacting a conventional polymeric additive (either alone or in solution) with solid iodine, e.g., iodine crystals, or by dissolving iodine in a solvent to form a solution and treating the polymeric additive with said solution, or by bubbling iodine vapor through the polymeric additive.
  • a conventional polymeric additive either alone or in solution
  • solid iodine e.g., iodine crystals
  • the temperature of treatment will usually be from 20 to 200 F., preferably 40 to 100 F., e.g., 60 F.
  • the treatment will generally last from 0.1 to 100 hours or more, usually from l to 72 hours, preferably from 2 to 48 hours, e.g., 24 hours.
  • the length of treatment will depend upon the quantities of reagents employed, temperature, degree of agitation, etc.
  • the pressure will usually be atmospheric, although suband super-atmospheric pressures may be used.
  • the iodine and polymeric additive are merely mixed together under the conditions just recited. If desired, the iodine can be pulverized or powdered to facilitate the treatment. The relative quantities of iodine and polymeric additive used will be determined by such factors as the amount of iodine desired in the final product, desired rate of treatment, etc.
  • iodine in a solvent to form a solution prior to treating a polymeric additive, such dissolution will generally be done at temperatures of from 20 to 200 F., usually from 40 to 100 F., e.g., 80 F. Generally the iodine will dissolve to the extent of from 0.1 to 100 grams of iodine per 100 ml. of solvent and more usually from 1 to 50 grams of iodine per 100 ml. of solvent.
  • Suitable solvents include, in general, any solvent which will not react with the polymer or iodine, i.e., an inert solvent, which is preferably a solvent for both the iodine and the polymer, and which can readily be removed from the polymer after the treatment is complete.
  • an inert solvent which is preferably a solvent for both the iodine and the polymer, and which can readily be removed from the polymer after the treatment is complete.
  • These solvents can generally be characterized as having a specific gravity of from 0.5 to 1.8 and a boiling point of from 30 to 250 F.
  • Suitable solvents include ethyl alcohol, benzene, carbon disulfide, cyclohexane, chloroform, diethyl ether, glycerol, carbon tetrachloride, and oils, as well as solvents containing nitrogen atoms, e.g., pyridine, quinoline or the amines. Of these, diethyl other is preferred.
  • the iodine-containing solution is then mixed with the polymeric additive and the treatment is conducted under the conditions previously outlined.
  • the resulting iodine-containing polymeric additive may then be purified by normal techniques such as filtration, evaporation, crystallization, etc. to remove the solvent and any unreacted iodine.
  • iodine vapor it will usually be bubbled through the polymeric additive, although other techniques may be used, e.g., spraying the polymer through iodine vapor.
  • spraying the polymer e.g., e.g., a spraying the polymer through iodine vapor.
  • the previously outlined conditions of temperature, pressure and time of treatment also apply when iodine vapor is used.
  • nitrogen or some other inert gas may be used to carry the unreacted iodine vapors away.
  • the amount of iodine will be from 20 to wt. percent, and most preferably from 40 to 80 wt. percent, of the iodine-containing polymer.
  • These iodine-containing polymeric additives may, in turn, be incorporated into lubricating oil compositions to give a total iodine concentration of from 0.005 to 3.0 wt. percent, preferably 0.01 to 0.8 wt. percent.
  • these additives may be added to oil concentrates in which case the iodine content will be proportionately higher.
  • the polymeric lubricant additives which can be improved by the addition of iodine thereto, may be homopolymers, that is, polymers consisting of a single constituent monomer, or they may be copolymers consisting of two or more constituent monomers. These polymers may be prepared by conventional polymerization or copolymerization techniques well known in the art. The preparation of such polymeric materials does not constitute a part of this invention.
  • the polymers useful in the present invention include oil soluble homopolymers and copolymers formed from C to C olefins and C to C ethylenically mono-unsaturated esters.
  • the molecular Weight (Staudinger) of these polymers will usually fall within the range of 300 to 500,000, e.g., 500 to 60,000.
  • the homopolymers are exemplified by the following:
  • Polymers of monoolefins which may be aliphatic or have an aromatic substituent, e.g., ethylene, propylene, isobutylene, alkyl styrene, etc.
  • Polymers of diolefins e.g., butadiene, isoprene, etc.
  • Polymers of vinyl esters e.g., vinyl 2-ethylhexoate, the vinyl ester of coconut acids, the vinyl ester of C Oxo acids made by the oxonation of tripropylene, etc.
  • vinyl ethers e.g., vinyl isobutyl ether, vinyl decyl ether, the vinyl ether of C Oxo alcohol made by the oxonation of C monoolefin (propylene-butylene copolymer), etc.
  • esters of cap-unsaturated dicarboxylic acids e.g.,. octyl fumar-ate, lauryl maleate, the aconitateand itaconate esters of mixed alcohols obtained by the V hydrogenationof coconut oil acids, etc.
  • copolymers are exemplified by the following:
  • Copolymers of various olefins e.g., ethylene and pro pylene; isobutylene and styrene; butadiene and isobutylene; butadiene and methyl styrene; etc.
  • Copolymers of olefins and unsaturated esters e.g., isoethyl methacrylate and octyl fumarate; methyl acrylate and dodecyl maleate;ootadecyl fumarate and octyl aconitate; methyl methacrylate and stearyl itaconate; isopropeny'l acetate and tetradecylacrylate, etc.
  • Copolymers of vinyl esters and unsaturated acid esters .e.g., vinyl acetate and fumarate esters of tallow alcohols; vinyl 2-ethyl butyrate and isodecyl maleate; isopropenyl acetate and the itaconic esters of coconut alcohols; etc.
  • Copolymers of three or more monomers e.g., the terpolymer of vinyl acetate, octyl fumarate and maleic anhydride, etc. 7
  • the preferred polymeric additives for use according to p the present invention include polybutene ,and its derivatives, e.g.', phosphosulfurized polybutene, and ethoxylated, hydrolyzed, phosphosulfurized polybutene.
  • the polybutene will generally have a molecular (Staudinger) of from 300 to 25,000, preferably 400to' 10,000, e.g., 800.
  • polymeric additives are'useful in lubricating compositions to improve the viscosity index, forvthickening, as pour-point depressants, for detergency, etc.
  • the homopolymers have one desirable property (in addition to the thickening characteristic)
  • the copolymers have two desirable properties
  • the terpolymers have three desir-able properties.
  • Example 1 One hundred grams of iodine crystals, 100 grams of polybutene having .a Staudinger molecular weight of were mixed together to'form a solution which was. then allowed to stand at room temperature, i.e., about 75 F. for 24 hours. Next, the solution was filtered through .filter paper to removeany excess iodine crystals. The filtrate was placed on a steam bath (about 160 F;) for about 3 hours to evaporate the ether. The final product (a dark viscous liquid) contained about 76 wt. percent iodine.
  • Example 2 A mixture of 100 grams of iodine and 200 grams of diethyl ether'as a 'solvent was mixed with 100 grams of a 'phosphosulfurized polybutene prepared from polybutene having a St-audinger molecular weight of about 780. This mixture was maintained at a temperature of about 70 for 24 hours. The final product was isolated usingthe technique described in Example 1. The product contained about 34 wt. percent iodine.
  • the phosphosulfurized polybutene used above was a commercially available material having a phosphorous con-tent within they range of 3-4 wt. percent and a sulfur content within the range of 6-7 wt. percent. This phosphosu-lfurized polybutene is oil-soluble, i.e., 2 wt. percent of the phosphosulfurized material is completely soluble in hexane'at 70 F.
  • iodine crystals 100 grams of an ethoxylated, hydrolyzed, phosphosulfur-ized polybutene weight room temperature, i.e., 75 F.,' for 24 hours.
  • Example 2 prepared from a polybutene having a Staudinger molecular weight of about 780, and 200 grams of diethyl other as a solvent were mixed together and allowed to stand at 0 Product recovery was similar to that employed in Example 1. The product contained about wt. percent iodine.
  • the ethoxylated, hydrolyzed, phosphosulfurized poly butene was prepared by first diluting a phosphosulfurized polybutene, such as that described in Example 2, with a mineral oil (such as a paralfinic distillate having a visvCosity of 112 SUS at ,100 F. and a viscosityv index of 113) to a 50% concentration. :The dilute mixture was then hydrolyzed at about 320 1F. with steam. The bydrolyzing reaction was controlled 'by observing the increase in acid number (units are mg. of KOH/gm.
  • other lubricating compositions were made by dissolving 1.0 wt. percent "of the untreated polymeric additives in the same -mineral oil.
  • the apparatus consists of a fixed metalball I /2 inch dia.) loaded against a rotating-steel cylinder (1% inch dia.).
  • the extent of metallic contact is determined by passing an electric current through the ball and cylinder and measuring both the continuous and the average electric, resistance between the contacting surfaces of the ball and cylinder.
  • the extent of metallic contact is expressed as thepercent of the time that metallic contact occurs in'a given period of time and is a measure of wear, i.e., the less the contact, the less the wear. Friction between the ball and the cylinder can be recorded simultaneously with metallic contact and is expressed in terms of grams of force.
  • Base oil a paraffinic lubricating oil having a 240 92 23 viscosity of 112 SUS at 100 F. and a VI of 113- 63 100 960 97 102 4, 000 99 329 Base oil plus 1% of the untreated polybutene of 240 92 28 Example 1 -7 40 89 960 100 103 4, 000 100 375 Base 011 plus 1% of the iodine-treated polybu- 240 1 12 tene of Example 1 960 2 34 4, 000 7 184 Base oil plus 1% of the untreated phosphosul- 240 100 27 furized polybutene of Example 2 50 112 960 100 102 4, 000 100 382 Base oil plus 1% of the iodine-treated phospho- 96 11 sulfurized polybutene of Example 2 200 316 960 100 28 4, 000 100 172 B asedoillplus1 171 1 of tlhe uiiftreateld eiihrgxyzlatedk 1y r0 yze
  • Example 4 It is apparent from Table II that the amount of iodine in the final product is increased when the initial ratio of A Senes of Samples deslgnated A to I was prepared by iodine to polybutene is increased. Also, the addition of the followmg Procedure to Illustrate the eflact of the Q0 the solvent appears to increase the amount of iodine iniodine/polybutene ratio as well as the inert solvent/ u 1 Polybutene ratio on the ultimate iodine content of the g figi igfg 55 p0 ymer' Compare specifically sample polymer. The procedure employed was as follows: one weight percent of Samples D, E, F and G were a.
  • the butane ether f i product is then heated to evaporate the cyclohexane to thereby leave the iodine-containing copolymer product. 0 100 100 0
  • Two weight percent of the iodine-containing polymer is 5 95 100 0. 52 then added to the base oil of Table I to form a lubricant g 22 188 3 2% having improved EP and antiwear properties.
  • the lubricating composition thus formed will have improved EP and antif riction properties.
  • iodine 'to polymeric lubricant additives results in lubricating compositions which are extremely effective in reducing friction and have greatly improved EP properties.
  • the addition of iodine according to the present invention does not appreciably affect the original properties of the polymers, e.g., VI improvement, etc. The net effect isto impart additional properties to the polymeric additives.
  • agents can also be used in the ultimate lubricating compositions. Additionally, other materials may be combined with these polymeric iodine-containing additives to produce additive'mixtures having other properties. Examples of these other agents include dyes, pour depressants, heat thickened fatty oils, sulfurized fatty oils, organo-metallic compounds, thickeners, viscosity index irnprovers, resins, rubber, other" polymers, colloidal solids, soaps, sludge dispersants and anti-oxidants. Numerous other agents will be obvious to those skilled in the art.
  • percent iodine in'an amount of said copolymer sufficient to.;.give an iodine concentration in said composition of 0,005 to 3.0 wt. percent iodine, said iodinated copolymer being formedby mixi-ng iodine with a copolymer of alkyl fumarate ester and ester of vinyl alcohol and'lowmolecular weight saturated fatty acid, said esters containing 4 to 30 carbon atoms and said :copolymer being a lubricating oil additive.
  • composition according to claim 1 wherein said iodinated polymer contains 40 to wt. percent iodine,
  • iodine concentration is .0110 .8 wt. percent

Description

United States Patent 3,184,413 POLYMERIC LUBRICATING OIL ADDITEVES CON- TAINING IODlNE AND USES THEREOF Michael J. Furey, Berkeley Heights, and Philip Zaybekian,
Elizabeth, NJ., assignors to Esso Research and Engineering Company, a corporation of Delaware No Drawing. Filed June 21, 1962, Ser. No. 204,043 2 Claims. (Cl. 252-56) This invention relates to lubricant additives. More specifically, this invention relates to polymeric lubricant additives containing iodine.
It is conventional to add polymers to lubricating oil, especially in formulating crankcase motor oils, for one or more of the following purposes: to increase the viscosity index of the oil; to lower the pour point of the oil; to thicken the oil; to impart detergency; or to improve the sludge-handling capacity of the oil. It has now been discovered that conventional polymeric lubricating oil additives can be treated with iodine to impart improved antifriction, extreme pressure (EP), and antiwear properties to them. Lubricant additives containing iodine and prepared according to the present invention will find utility wherever lubricant additives having antifriction, antiwear, and EP properties are desired, e.g., automobile crankcase lubrication, bearing lubrication, gear lubrication, etc.
PREPARATION The treatment with iodine may be made by contacting a conventional polymeric additive (either alone or in solution) with solid iodine, e.g., iodine crystals, or by dissolving iodine in a solvent to form a solution and treating the polymeric additive with said solution, or by bubbling iodine vapor through the polymeric additive.
The temperature of treatment will usually be from 20 to 200 F., preferably 40 to 100 F., e.g., 60 F. The treatment will generally last from 0.1 to 100 hours or more, usually from l to 72 hours, preferably from 2 to 48 hours, e.g., 24 hours. The length of treatment will depend upon the quantities of reagents employed, temperature, degree of agitation, etc. The pressure will usually be atmospheric, although suband super-atmospheric pressures may be used.
When a polymeric additive is treated with solid iodine, the iodine and polymeric additive are merely mixed together under the conditions just recited. If desired, the iodine can be pulverized or powdered to facilitate the treatment. The relative quantities of iodine and polymeric additive used will be determined by such factors as the amount of iodine desired in the final product, desired rate of treatment, etc.
If it is desired to dissolve the iodine in a solvent to form a solution prior to treating a polymeric additive, such dissolution will generally be done at temperatures of from 20 to 200 F., usually from 40 to 100 F., e.g., 80 F. Generally the iodine will dissolve to the extent of from 0.1 to 100 grams of iodine per 100 ml. of solvent and more usually from 1 to 50 grams of iodine per 100 ml. of solvent. Suitable solvents include, in general, any solvent which will not react with the polymer or iodine, i.e., an inert solvent, which is preferably a solvent for both the iodine and the polymer, and which can readily be removed from the polymer after the treatment is complete. These solvents can generally be characterized as having a specific gravity of from 0.5 to 1.8 and a boiling point of from 30 to 250 F.
3,184,413 Patented May 18, 1965 Suitable solvents include ethyl alcohol, benzene, carbon disulfide, cyclohexane, chloroform, diethyl ether, glycerol, carbon tetrachloride, and oils, as well as solvents containing nitrogen atoms, e.g., pyridine, quinoline or the amines. Of these, diethyl other is preferred. The iodine-containing solution is then mixed with the polymeric additive and the treatment is conducted under the conditions previously outlined. The resulting iodine-containing polymeric additive may then be purified by normal techniques such as filtration, evaporation, crystallization, etc. to remove the solvent and any unreacted iodine.
Alternatively, if iodine vapor is to be employed, it will usually be bubbled through the polymeric additive, although other techniques may be used, e.g., spraying the polymer through iodine vapor. The previously outlined conditions of temperature, pressure and time of treatment also apply when iodine vapor is used. When iodine vapor is bubbled through a polymeric additive, nitrogen or some other inert gas may be used to carry the unreacted iodine vapors away.
Polymeric additives containing from 10 to 90 wt. percent iodine, based on the total weight of iodine and polymer, generally provide the most beneficial results although lower iodine concentrations may be used, e.g., 0.5 wt. percent. Preferably the amount of iodine will be from 20 to wt. percent, and most preferably from 40 to 80 wt. percent, of the iodine-containing polymer. These iodine-containing polymeric additives may, in turn, be incorporated into lubricating oil compositions to give a total iodine concentration of from 0.005 to 3.0 wt. percent, preferably 0.01 to 0.8 wt. percent. Alternatively, these additives may be added to oil concentrates in which case the iodine content will be proportionately higher.
POLYMERIC ADDITIVES WHICH CAN BE TREATED WITH IODINE The polymeric lubricant additives, which can be improved by the addition of iodine thereto, may be homopolymers, that is, polymers consisting of a single constituent monomer, or they may be copolymers consisting of two or more constituent monomers. These polymers may be prepared by conventional polymerization or copolymerization techniques well known in the art. The preparation of such polymeric materials does not constitute a part of this invention.
The polymers useful in the present invention include oil soluble homopolymers and copolymers formed from C to C olefins and C to C ethylenically mono-unsaturated esters. The molecular Weight (Staudinger) of these polymers will usually fall within the range of 300 to 500,000, e.g., 500 to 60,000.
The homopolymers are exemplified by the following:
Polymers of monoolefins which may be aliphatic or have an aromatic substituent, e.g., ethylene, propylene, isobutylene, alkyl styrene, etc.
Polymers of diolefins, e.g., butadiene, isoprene, etc.
Polymers of esters of acrylic and of methacrylic acids, e.g., decyl acrylate, lauryl methacrylate, mixed C to C rnethacrylates, etc.
Polymers of vinyl esters, e.g., vinyl 2-ethylhexoate, the vinyl ester of coconut acids, the vinyl ester of C Oxo acids made by the oxonation of tripropylene, etc.
Polymers of vinyl ethers, e.g., vinyl isobutyl ether, vinyl decyl ether, the vinyl ether of C Oxo alcohol made by the oxonation of C monoolefin (propylene-butylene copolymer), etc.
Polymers of esters of cap-unsaturated dicarboxylic acids, e.g.,. octyl fumar-ate, lauryl maleate, the aconitateand itaconate esters of mixed alcohols obtained by the V hydrogenationof coconut oil acids, etc.
The copolymers are exemplified by the following:
Copolymers of various olefins, e.g., ethylene and pro pylene; isobutylene and styrene; butadiene and isobutylene; butadiene and methyl styrene; etc.
Copolymers of olefins and unsaturated esters, e.g., isoethyl methacrylate and octyl fumarate; methyl acrylate and dodecyl maleate;ootadecyl fumarate and octyl aconitate; methyl methacrylate and stearyl itaconate; isopropeny'l acetate and tetradecylacrylate, etc.
Copolymers of vinyl esters and unsaturated acid esters, .e.g., vinyl acetate and fumarate esters of tallow alcohols; vinyl 2-ethyl butyrate and isodecyl maleate; isopropenyl acetate and the itaconic esters of coconut alcohols; etc. Copolymers of three or more monomers, e.g., the terpolymer of vinyl acetate, octyl fumarate and maleic anhydride, etc. 7
The preferred polymeric additives for use according to p the present invention include polybutene ,and its derivatives, e.g.', phosphosulfurized polybutene, and ethoxylated, hydrolyzed, phosphosulfurized polybutene. The polybutene will generally have a molecular (Staudinger) of from 300 to 25,000, preferably 400to' 10,000, e.g., 800.
As previously indicated, polymeric additives, typified by the above, are'useful in lubricating compositions to improve the viscosity index, forvthickening, as pour-point depressants, for detergency, etc. Generally, the homopolymers have one desirable property (in addition to the thickening characteristic), the copolymers have two desirable properties, and the terpolymershave three desir-able properties. Y e
EXAMPLES The present invention will be further understood by reference to the following examples .which include a preferred embodiment of this invention.
Example 1 One hundred grams of iodine crystals, 100 grams of polybutene having .a Staudinger molecular weight of were mixed together to'form a solution which was. then allowed to stand at room temperature, i.e., about 75 F. for 24 hours. Next, the solution was filtered through .filter paper to removeany excess iodine crystals. The filtrate was placed on a steam bath (about 160 F;) for about 3 hours to evaporate the ether. The final product (a dark viscous liquid) contained about 76 wt. percent iodine.
Example 2 A mixture of 100 grams of iodine and 200 grams of diethyl ether'as a 'solvent was mixed with 100 grams of a 'phosphosulfurized polybutene prepared from polybutene having a St-audinger molecular weight of about 780. This mixture was maintained at a temperature of about 70 for 24 hours. The final product was isolated usingthe technique described in Example 1. The product contained about 34 wt. percent iodine. The phosphosulfurized polybutene used above was a commercially available material having a phosphorous con-tent within they range of 3-4 wt. percent and a sulfur content within the range of 6-7 wt. percent. This phosphosu-lfurized polybutene is oil-soluble, i.e., 2 wt. percent of the phosphosulfurized material is completely soluble in hexane'at 70 F.
Example 3,
One hundred grams of iodine crystals, 100 grams of an ethoxylated, hydrolyzed, phosphosulfur-ized polybutene weight room temperature, i.e., 75 F.,' for 24 hours.
prepared from a polybutene having a Staudinger molecular weight of about 780, and 200 grams of diethyl other as a solvent were mixed together and allowed to stand at 0 Product recovery was similar to that employed in Example 1. The product contained about wt. percent iodine.
The ethoxylated, hydrolyzed, phosphosulfurized poly butenewas prepared by first diluting a phosphosulfurized polybutene, such as that described in Example 2, with a mineral oil (such as a paralfinic distillate having a visvCosity of 112 SUS at ,100 F. and a viscosityv index of 113) to a 50% concentration. :The dilute mixture was then hydrolyzed at about 320 1F. with steam. The bydrolyzing reaction was controlled 'by observing the increase in acid number (units are mg. of KOH/gm. of sample as determined by Method ASTM-D-974) which went from an initial value of about8 to a value of about 50 upon completion of the hydrolysis. The hydrolyzed product was then treated'with ethylene oxide at about 320 F. to reduce the acid number from about 50 to less than 1. Theamount of ethylene oxide required for this step was roughly equalto 1 6% by weight based on the amount of the-phosphosulfuri zed polybutene employed.
Lubricating oil compositions'were made by dissolving the iodine-treated polymers of=Examples 1-3 in a paraffinic' lubricating oil having a viscosity of 112 SUS at 100 and a viscosityindex of 113. For comparison, other lubricating compositions were made by dissolving 1.0 wt. percent "of the untreated polymeric additives in the same -mineral oil. These various compositions, together with thebase oil, per se, were tested for their load carrying ability in a 4-ball EP test and in the ball and cylinder ap- -paratus which is hereinafter'described. The results of V metallioCOHtflCt and frictionlbetween sliding lubricated (about 780 and 200 grams. of diethyl other as a solvent 7 surfaces. A complete-description of the apparatus can be found in a paper entitled Metallic Contact and Friction Between Sliding Surfaces by M. J Furey, presented at the 1960 Joint ASLE-ASME Lubrication Conference, October 19, 1960, in Boston, Massachusetts. This paper has been published by the American Society of 'Lubrication Engineers, 5 North Wabash Avenue, Chicago 2, Illinois, under the above-noted titlein the ASLE Transactions, vol. 4, No. 1, pages 1-11,'Apr il 1961.
Basically the apparatus consists of a fixed metalball I /2 inch dia.) loaded against a rotating-steel cylinder (1% inch dia.). The extent of metallic contact is determined by passing an electric current through the ball and cylinder and measuring both the continuous and the average electric, resistance between the contacting surfaces of the ball and cylinder. The extent of metallic contact is expressed as thepercent of the time that metallic contact occurs in'a given period of time and is a measure of wear, i.e., the less the contact, the less the wear. Friction between the ball and the cylinder can be recorded simultaneously with metallic contact and is expressed in terms of grams of force.
Referring now to TableI, the addition of the iodinetreated polybutene of Example 1 to the base oil resulted in a lubricating composition having highly improved EP properties, as wellras markedly reducing both metallic contact and friction.
The addition of the iodine-treated phosphosulfurized polybutene of Example 2 to the base oil resulted in highly improved EP characteristics and markedly reduced the friction.
TABLE I 4-ba11 EP test 1 Org.) Ball on cylinder test (240 r.p.m. for
32 min.)
Load Percent Friction Seize Weld (gins) metallic (g-ms.)
contact Base oil: a paraffinic lubricating oil having a 240 92 23 viscosity of 112 SUS at 100 F. and a VI of 113- 63 100 960 97 102 4, 000 99 329 Base oil plus 1% of the untreated polybutene of 240 92 28 Example 1 -7 40 89 960 100 103 4, 000 100 375 Base 011 plus 1% of the iodine-treated polybu- 240 1 12 tene of Example 1 960 2 34 4, 000 7 184 Base oil plus 1% of the untreated phosphosul- 240 100 27 furized polybutene of Example 2 50 112 960 100 102 4, 000 100 382 Base oil plus 1% of the iodine-treated phospho- 96 11 sulfurized polybutene of Example 2 200 316 960 100 28 4, 000 100 172 B asedoillplus1 171 1 of tlhe uiiftreateld eiihrgxyzlatedk 1y r0 yze ,p osp 10811 urize po y u once Example3 56 100 3g Base gilhplgs 1% oil tltile ioginel-ltrreater etllro xylate y rolyze p osp 0s urize p0 y utene of Example 3 224 280 3g 3g 1 Steel-on-steel at 1800 rpm. 1 No seize, no weld at 580 kg.
Example 4 It is apparent from Table II that the amount of iodine in the final product is increased when the initial ratio of A Senes of Samples deslgnated A to I was prepared by iodine to polybutene is increased. Also, the addition of the followmg Procedure to Illustrate the eflact of the Q0 the solvent appears to increase the amount of iodine iniodine/polybutene ratio as well as the inert solvent/ u 1 Polybutene ratio on the ultimate iodine content of the g figi igfg 55 p0 ymer' Compare specifically sample polymer. The procedure employed was as follows: one weight percent of Samples D, E, F and G were a. The iodine crystals, polybutene and diethyl ether were added to the same base oil shown in Table I, supra, and Weighed into separate flasks; were tested in the same ball and cylinder apparatus. 12. These materials were mixed together in one of the Samples E, F, and G were also given a 4-ball EP test.
flasks by manually shaking the flask; Those test results are summarized in Table III.
TABLE III Ball on cylinder test (240 rpm. for 32 min.) 4-bal1EP test 1 (kg.)
Sample Percent metallic Friction (grams) contact at load of at load of Seize Weld 240 gms. 960 grns. 240 gms. 960 gms.
Base oil per se 91 99 25 102 Base oil plus 1 weight percent D 46 100 15 71 Base oil plus 1 weight percent E 10 0 9 28 Base 011 plus 1 weight percent F 0 90 12 37 Base oil plus 1 weight percent G 4 78 14 40 l Stcel-on-steel at 1800 rpm. c. The mixture was allowed to stand for about 24 hours Table III clearly illustrates the benefits to be obtained at room temperature (about 75 F.); from using the iodine-treated polymers of the present ind. The mixture was next filtered through filter paper to vention in terms of reducing the percent metallic contact remove any excess iodine; (Le, wear) and friction, as well as improving the EP 0. The diethyl ether was evaporated from the filtrate by properties.
placing the filtrate on a steam bath (160 F.) for 48 Example 5 hours. The quantities used and analyses of the samples are Elght hundred fifty grams of cyclohexane as an mart t 1 solvent and 200 grams of a copolymer of equi-molar pro- Shown below m T113 6 H portions of butadiene and methylstyrene having a Staud- TABLE H inger molecular weight of about 3,000 are mixed together. Weightpep Gaseous iodine is bubbled through the mixture until 30 Sample Gms. r2 Gms.polydiethyl cent iodine wt. percent of iodine is incorporated in the polymer. The butane ether f i product is then heated to evaporate the cyclohexane to thereby leave the iodine-containing copolymer product. 0 100 100 0 Two weight percent of the iodine-containing polymer is 5 95 100 0. 52 then added to the base oil of Table I to form a lubricant g 22 188 3 2% having improved EP and antiwear properties. 3 2 i i Example 6 10 59.0 28 g 8 (2) M9 One hundred grams of iodine crystals, 100 grams of the 25 75 o 0.80 terpolymer of alkyl fumarate, vinyl acetate and maleic anhydride (a lubricating oil polymer marketed by the New York, under the trade name Paratone 430) and A 200 grams of carbon tetrachloride as an inert solvent are mixed together and allowed to stand atroom temperature;
(72 F.) for about 72 hours. Product recovery'is similar to that of Example 1. amount of iodine within'the range contemplated by this invention. .When the iodine-containing polymerisfadded to a synthetic lubricating oil [bis ('2-et l1ylhexyl) sebacate] The product will "contain fan 300 to 500,000. molecular Weight containing to 90 wt.
in an amount-sufficient to providea total iodine content of about 0.5 wt. percent, the lubricating composition thus formed will have improved EP and antif riction properties.
Thus, it is apparent that the addition of iodine 'to polymeric lubricant additivesresults in lubricating compositions which are extremely effective in reducing friction and have greatly improved EP properties. The addition of iodine according to the present invention does not appreciably affect the original properties of the polymers, e.g., VI improvement, etc. The net effect isto impart additional properties to the polymeric additives.
It should be realized that other agents can also be used in the ultimate lubricating compositions. Additionally, other materials may be combined with these polymeric iodine-containing additives to produce additive'mixtures having other properties. Examples of these other agents include dyes, pour depressants, heat thickened fatty oils, sulfurized fatty oils, organo-metallic compounds, thickeners, viscosity index irnprovers, resins, rubber, other" polymers, colloidal solids, soaps, sludge dispersants and anti-oxidants. Numerous other agents will be obvious to those skilled in the art.
While the above invention has been described with a certain degree of particularity, .it is'realized that various additional modifications and adaptations can be made within the spirit and scope of the'invention as hereinafter claimed.
percent iodine in'an amount of said copolymer sufficient to.;.give an iodine concentration in said composition of 0,005 to 3.0 wt. percent iodine, said iodinated copolymer being formedby mixi-ng iodine with a copolymer of alkyl fumarate ester and ester of vinyl alcohol and'lowmolecular weight saturated fatty acid, said esters containing 4 to 30 carbon atoms and said :copolymer being a lubricating oil additive.
2. A composition according to claim 1, wherein said iodinated polymer contains 40 to wt. percent iodine,
wherein said iodine concentration, is .0110 .8 wt. percent,
References Cited by the Examiner UNITED STATES PATENTS DANIEL E. WYMAN, Primary Examiner. JULIUS GREENWALD, Examiner.

Claims (1)

1. A LUBRICATING COMPOSITION COMPRISING A MAJOR AMOUNT OF LUBRICATING OIL AND AN IODINATED COPOLYMER OF 300 TO 500,000 MOLECULAR WEIGHT CONTAINING 10 TO 90 WT. PERCENT IODINE IN AN AMOUNT OF SAID COPOLYMER SUFFICIENT TO GIVE AN IODIEN CONCENTRATION IN SAID COMPOSITION OF 0.005 TO 3.0 WT. PERCENT IODINE, SAID IODINATED COPOLYMER BEING FORMED BY MIXING IODINE WITH A COPOLYMER OF ALKYL FUMARATE ESTER AND ESTER OF VINYL ALCOHOL AND LOW MOLECULAR WEIGHT SATURATED FATTY ACID, SAID ESTERS CONTAINING 4 TO 30 CARBON ATOMS AND SAID COPOLYMER BEING A LUBRICATING OIL ADDITIVE.
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Cited By (9)

* Cited by examiner, † Cited by third party
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US3515670A (en) * 1967-09-11 1970-06-02 Gen Electric Iodoethyl-substituted organosilicon compound lubricating compositions and use thereof
US3767576A (en) * 1967-09-11 1973-10-23 Gen Electric Lubricating compositions containing halogen and alkoxy, acyloxy, or hydroxy groups
US4085056A (en) * 1977-03-22 1978-04-18 Bray Oil Co. Inc. Inhibitor composition containing an oligomer oil
US4826615A (en) * 1985-06-07 1989-05-02 Exxon Chemical Patents Inc. Lubricating oil composition containing dual additive combination for low temperature viscosity improvement (PTF-004)
US4891145A (en) * 1985-01-31 1990-01-02 Exxon Chemical Patents Inc. Lubricating oil composition
US4957650A (en) * 1985-06-07 1990-09-18 Exxon Chemical Patents Inc. Lubricating oil composition containing dual additive combination for low temperature viscosity improvement
EP0665242A1 (en) * 1994-01-28 1995-08-02 The Lubrizol Corporation Treatment of organic compounds to reduce chlorine level
WO1996020264A1 (en) * 1992-12-29 1996-07-04 Genvol Corp. Esteblishment Method of stabilising motor oil
US5674819A (en) * 1995-11-09 1997-10-07 The Lubrizol Corporation Carboxylic compositions, derivatives,lubricants, fuels and concentrates

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US2298833A (en) * 1940-03-28 1942-10-13 Jasco Inc Lubricant
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GB807737A (en) * 1956-07-27 1959-01-21 Exxon Research Engineering Co Mineral oil compositions
US2920064A (en) * 1954-07-29 1960-01-05 Phillips Petroleum Co Process for halogenation of polymers
US2927895A (en) * 1955-09-20 1960-03-08 Minnesota Mining & Mfg Novel composition of improved lubricating properties comprising a fluorochloro polymer
US2992988A (en) * 1954-11-23 1961-07-18 Minnesota Mining & Mfg Grease composition comprising a solution of a chlorotrifluoroethylene vinylidene fluoride copolymer in a low molecular weight chlorotrifluoroethylene polymer
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US2155204A (en) * 1937-08-17 1939-04-18 Lubri Zol Dev Corp Lubricant
US2126590A (en) * 1938-02-24 1938-08-09 Lubri Zol Dev Corp Lubricating oil
US2308622A (en) * 1939-03-09 1943-01-19 Lubri Zol Dev Corp Lubricating oil
US2225318A (en) * 1939-08-26 1940-12-17 Standard Oil Dev Co Lubricating composition
US2298833A (en) * 1940-03-28 1942-10-13 Jasco Inc Lubricant
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US2992988A (en) * 1954-11-23 1961-07-18 Minnesota Mining & Mfg Grease composition comprising a solution of a chlorotrifluoroethylene vinylidene fluoride copolymer in a low molecular weight chlorotrifluoroethylene polymer
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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3515670A (en) * 1967-09-11 1970-06-02 Gen Electric Iodoethyl-substituted organosilicon compound lubricating compositions and use thereof
US3767576A (en) * 1967-09-11 1973-10-23 Gen Electric Lubricating compositions containing halogen and alkoxy, acyloxy, or hydroxy groups
US4085056A (en) * 1977-03-22 1978-04-18 Bray Oil Co. Inc. Inhibitor composition containing an oligomer oil
US4891145A (en) * 1985-01-31 1990-01-02 Exxon Chemical Patents Inc. Lubricating oil composition
US4826615A (en) * 1985-06-07 1989-05-02 Exxon Chemical Patents Inc. Lubricating oil composition containing dual additive combination for low temperature viscosity improvement (PTF-004)
US4957650A (en) * 1985-06-07 1990-09-18 Exxon Chemical Patents Inc. Lubricating oil composition containing dual additive combination for low temperature viscosity improvement
WO1996020264A1 (en) * 1992-12-29 1996-07-04 Genvol Corp. Esteblishment Method of stabilising motor oil
EP0665242A1 (en) * 1994-01-28 1995-08-02 The Lubrizol Corporation Treatment of organic compounds to reduce chlorine level
US5708097A (en) * 1994-01-28 1998-01-13 The Lubrizol Corporation Treatment of organic compounds to reduce chlorine level
US5674819A (en) * 1995-11-09 1997-10-07 The Lubrizol Corporation Carboxylic compositions, derivatives,lubricants, fuels and concentrates

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